JPH03200154A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve water repellency and resistance to chemicals without lowering necessary surface hardness by forming a protective layer composed essentially of a specified epoxysilane compound, a specified alkylalkoxysilane compound, a specified perfluoroalkylsilane compound, and a specified aminosilane compound. CONSTITUTION:The protective layer to be formed on the organic photoconductive layer is composed essentially of the epoxysilane compound of formula I or II, the alkylalkoxysilane compound of formula III, the fluoroalkylsilane compound of formula IV, and the aminosilane compound of formula V or VI, In formulae I - VI R<1> is 1 - 6 C straight or branched alkyl; R<2> is 1 - 4 C straight or branched alkyl; R<3> is same as R<2>; R<4> is 1 - 8 C straight or branched alkyl; R<5> is 2 - 4 C straight or branched alkyl; n1 is 0 or 1; n2 is 0, 1, or 2; and n3 is an integer of 0 - 9, thus permitting water repellency and resistance to chemicals to be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor that is highly durable and has excellent environmental resistance.

[Prior Art] Organic compound photoconductive layers are used as photoconductive layers for electrophotography. The organic photoconductive layer in which the charge generation layer is provided on the support side and the charge transfer F71 layer is provided on the surface side is a photoconductive layer made of thiolene and selenium tellurium compounds, and the surface is thickly covered with a charge transfer layer that also serves as a protective layer. It is considered to be more durable.

However, as printers, copiers, etc. have become faster, their cleaning mechanisms have become more powerful, resulting in poor charging performance and
In addition, ozone generated by corona discharge during negative charging or adhesion of paper dust due to transfer causes deterioration of the surface liquid, resulting in poor image quality.

In order to improve these, firstly, on top of the photoelectric layer,
A method of improving durability by providing a transparent protective layer has been proposed. Examples of materials used to form this protective layer include polymeric materials such as polyurethane, polyester, polycarbonate, and polyethylene.

Hydrolysates of silane coupling agents have also been reported as materials for transparent protective layers, but this technology uses methyltrimethoxysilane, vinyltriethoxysilane, γ-
Glycidoxy I lobiltrimethoxysilane, γ-aminopropyltrimethoxysilane, detraethoxysilane, etc., alone or in combination, are hydrolyzed by adding an acid or alkali catalyst, and this is applied to the photoconductive layer and dried. A single layer of protection is formed by using the same method (Japanese Patent Publication No. 58-3223).

In addition, a method of incorporating a fluorine-containing silane coupling agent into the protective layer has recently been proposed (Japanese Patent Application Laid-Open No. 61-2059
50).

In this method, a fluorine compound and a fluorine silane coupling agent are added and mixed to a thermal HiJ plastic resin and a curable resin to form a protective layer.

Furthermore, a protective layer containing (1) a non-catalytic hydrolyzate of a composition consisting of a boxysilane compound, an alkyl alkoxy compound and an aminosilane compound has recently been invented by Mizuben 1^ (Japanese Patent Laid-Open No. 1-200366).

[Problems to be Solved by the Invention] However, the above-mentioned materials such as polyurethane, polyester, polycarbonate, and polyethylene cannot be said to have sufficient durability, and in particular, photoreceptors provided with this type of transparent protective layer are susceptible to humidity and changes in humidity. This has the disadvantage that the effect appears on the image, making it impossible to obtain a clear and stable image.

In addition, in the case of a hydrolyzate of a silane coupling agent, when forming a protective layer, it is common to add the above-mentioned catalyst to advance the hydrolysis reaction. This has the drawback that it reduces the resistance value, causing image blurring under high temperature and high humidity conditions, making it impossible to obtain clear images. There is a problem in that addition of these compounds does not provide a protective layer with sufficient hardness.

It allows the hydrolysis reaction to proceed without adding a catalyst, cures at a relatively low temperature (around 100°C), and has sufficient hardness. ! It is also possible to obtain a layer, but in this case, for example, in the case of a selenium photoreceptor, crystallization is slow to be promoted, resulting in a decrease in the performance of the photoreceptor. Therefore, it is also necessary to adjust the curing temperature of the protective layer in order to maintain the performance of the photoreceptor, which is a difficult problem.

Regarding the last invention using a non-catalytic hydrolyzate, some problems have been pointed out in terms of water repellency and chemical resistance.

The present invention has been developed by applying a specific chemical on top of the organic photoconductive layer in order to slightly eliminate the problems of the conventional and prior art techniques and to improve water repellency and chemical resistance while maintaining the necessary surface hardness. It is an object of the present invention to provide a photoreceptor for electronic η calculation in which a protective layer is provided.

[Means to Solve the Problem 1] The inventors of the present invention have repeatedly studied the aspects of reducing the energy and surface strength of the organic light 81 electric material surface, and have developed a specific chemical that does not have an electrical effect. The perfluoroalkyl group in the composition lowers the energy of the surface, and the decrease in surface strength due to the inclusion of the nitrogen-containing silane coupling agent is reinforced with an alkyl alkoxysilane compound having a tri- or tetrafunctional group, resulting in sufficient hardness. A low-energy surface protective layer with a thermosetting liquefied film was formed.

That is, in the electrophotographic photoreceptor of the present invention, an organic photoconductive layer is provided on a conductive support.
On the layer, (a) at least one type of epoxysilane compound selected from the following group A, (b) at least one alkyl alkoxysilane compound selected from the following eight groups, (iii) at least one type of alkyl alkoxysilane compound selected from the following group C. and (d) at least one aminosilane compound selected from the sublayer group. , 耶(R'). Si (OR)4-n (J:CF3 (CF2)n2 (cH2)2
(R), 1SR2 [) 3 guns: +12 N RSt R3R2 (OR) 3-nl, 42 N-1<-Nt+-1<"However, in the above - Sailor, 1) 1 has a carbon number of 6 or less straight-chain or branched alkyl or C112CI-1=CI-CH2C112-, and R
2 is a straight chain or branched alkyl group having 4 or less carbon atoms,
R3 is a straight chain or branched alkyl group having 4 or less carbon atoms or an OR"° group, R3' is a straight chain or branched alkyl group having 4 or less carbon atoms, and R4 is a straight chain or branched alkyl group having 8 or less carbon atoms. It is a branched alkyl group, R5 is a straight chain or branched alkyl group having 2 to 4 carbon atoms, n is an integer of 1 or less, n is an integer of 2 or less, and n2 is an integer of 9 or less. .

The photoreceptor of the present invention has an organic leading conductive layer on a conductive support and furthermore has the above-mentioned 7Ml! 1, but
In particular, the organic photo8I conductive layer is not made into a single layer, but is divided into a charge generation layer and a charge transfer layer, and the charge generation layer, charge transfer layer, and retention layer are placed on a conductive support in this order as shown in Figure 1. There are those in which layers are laminated, and there are those in which only the order of the charge generation layer and charge transfer layer 1a is reversed.

For convenience, the explanation will be summarized according to the embodiment shown in FIG.
This photoreceptor has a charge generation layer 2 on a conductive support 1 made of metal such as aluminum, copper, or stainless steel.
Organic pigments such as metal phthalocyanine and azo dyes are used as organic pigments, and metal oxides such as aluminum oxide, polyurethane, high basol such as cellulose, bilibinylidene, etc. are used between the charge generation layer and the support material. Polymeric substances, hydrazone derivatives, oxysil derivatives, and other substances are used, and these may be combined with adhesive materials such as polymethyl methacrylate, polycarbonate, and polyester to form a layer.

The methods used include the DIP method, the spinner method, the spray method, and the Langmuir project method.

The composition mainly composed of a silane compound used in this case is thermosetting, and examples of the compound and preferred mixing ratio are as follows.

Examples of the compound represented by -Funenin include A 8Y
For β-glycidoxyethyl brobyl dibroboxysilane, β-glycidoxyethyl brobyl dibutoxysilane, γ-glycidoxyethyl brobyl dibutoxysilane, γ-glycid 1 thilbyldimethoxysilane, γ-glycid 1 diethylpropyl jetoxysilane, γ-glycid 1 Examples include siezylprobyl dibutoxysilane, γ-glycidol-1-szydylbrobyl dibutoxysilane, and the like.

Examples of B6 include monomethyltrimethoxysilane, monomethyltriethoxysilane, mono1-methyltrimethoxysilane, monoethyltriethoxysilane, tetramethoxysilane, tetramethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

As mentioned above, compounds of n≦1 are used as the compounds of Group 8 in order to prevent the surface hardness from decreasing due to the addition of the fluorine-containing silane coupling agent of Group 0. In addition to this, a furkylfurkoxysilane compound in which n is 3 to 1 can also be used in addition as appropriate. Examples include dimethyldimethoxysilane, dimethyljethoxysilane, diethyldimethoxysilane, diethyljethoxysilane, and the like.

Next, as compounds of group 0, γ, T, γ-triphropropyltrimethoxysilane CF3(C112)2S i (OCH3)3, heptafluorobenpurtrimethoxysilane C]:3(CF2)
2(C11□)2S1(OC113)3, nonafluorohexyltrimethoxysilane CF3(Cl:2)3(CI
□)2S i (OC++3>3, tridecafloO octyltrimethoxysilane CF3 (C112), (CH2
)2Si(OCH3)3, heptadecafluorodecyltrimethoxysilane CF3(Cr2)7(CI-12>,,
S r (OC+-13>3, triflo1]propyltriethoxysilane C'3 (CI4□>23 l (
OC2H5) 3, nonafluorohexyltriethoxysilane CF3 (CF2)3 (CI-12>, Si
(QC2II5)3, heneicosafluorododecyltrimethoxysilane CF3 (CF2>9(C1l,, )2
S i (QC2It5)3, CF3 (CF12
)2 S i (OCH3)2 , hebutadecafluorodecylmethyldimei~xysilane CF3(C'2
)7(CH2)2Si(OCH3)2,4naphropentanoyloxypbyltrimethoxysilane C'3 (C[2,)3C○0(C)12)3Si (
()C113) 3, Penta Y Kanorolo A ctanoyloxybrobyl i-rimethoxysilane Cl5 (CI-2>6 Coo (CII2) 3
S i (OCH3)3, Tsuno-noro[]pentanoylthiopropyltrimethoxysilane C)-3(C'2)3CO8(C112)3Si(OC
I'3) 3, pentadecaf 1 colooctylamidopropyl trime 1 - xysilane CI-'3 ((]F2)6CONH(CI2)3
S i (OCLI3)3, heptadecafluorodecylthioethyltrimethoxysilane CI-3 (C[2)7CH2)2S (C
(]2)2S i (OCH3)3, 41, etc. are used.

For D-intoxication, aminomethyltrimethoxysilane, aminemethyltriethoxysilane, aminomethylbrobogysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltributoxysilane, N-β-aminoethyl-γ-amino Examples include propyl trime-1 to xysilane. The composition ratio is HCl2 as a catalyst, l'cj! 0.01 to 0.1 parts by volume of a strong acid such as 0.04 may be used, and 1 to 6 parts by volume of water is further added to carry out hydrolysis, and an organic solvent is added to adjust the concentration of the hydrolyzate.

However, for compositions where hydrolysis ends instantly, hydrolysis is performed by adding 1 to 6 parts by volume of an organic solvent such as alcohol after mixing with water, and the concentration is adjusted by adding the same organic solvent used in hydrolysis. do.

The organic solvent added during or after hydrolysis is preferably a hydrophilic one, and methanol, ethanol, propatool, dioxane, methyl cellosolve, ethyl cellosolve, etc. can be used. The total amount of these organic solvents added is preferably 50 to 300 parts by volume. This solution containing an organic solvent is applied onto the organic compound photoconductive layer and cured by heating. The heating and curing temperature is 50°C to 100°C.
Hardening is possible in the range of .

In the present invention, the silane compounds of each family are chemically dehydrated and polymerized using water containing a catalyst and an organic solvent as necessary to form a strong molecular layer. be.

The protective layer formed according to the present invention provides the following advantages to the organic photoreceptor.

(1) In an organic photoreceptor, the surface deteriorates in an ozone atmosphere due to negative charging, resulting in image blurring. However, if a protective layer is provided on the surface, the surface of the photoreceptor will not deteriorate and the resolution will not deteriorate.

(2) When the blade is polished by cleaning or the like, the marks appear as streaks on the image. In this case, if a protective layer is provided on the surface, the charging voltage will not change locally, and
It is possible to obtain a photoreceptor that is not affected in any way.

Further, the IFJ thickness of the protective layer of the present invention is preferably 0.3 to 2 μm.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Example 1 β-(3,4-epoxycyclohexyl)nibrutrimethoxysilane 4.8 parts by volume, dimethyldimethoxysilane 2.4 parts by volume, tetramethoxysilane 2.4 parts by volume, γ
,γ. r-trifluoropropyltrimethoxysilane2.
4 parts by volume, 1 part γ-aminopropyltrinidoxysilane
．． 2 capacity parts and HCj! 0.1 volume part of the mixture was mixed, 1.2 volume parts of water and 1.2 volume parts of ethanol were added thereto, and the mixture was vigorously stirred at room temperature to proceed with the hydrolysis reaction, and then 50 volume parts of ethanol was added thereto. The coating solution for forming the 1C protective layer was vj4%l. Next, the above-mentioned coating solution for forming three protective layers was applied onto a known electrophotographic photoreceptor in which the compound II was provided on an aluminum support, and the coating solution was heated at 100° C. for 2 hours to form a transparent wear-resistant protective layer. A layer was formed.

The pλ diameter of this protective layer was 1.0 μm.

As a result of a peel test of the adhesiveness of the protective layer to the photoreceptor using cellophane tape, no peeled portion was observed. In addition, the hardness of the protective layer was examined using the pencil hardness method8)1
Met. Next, as a result of applying a known method to an electrophotographic method consisting of charging, exposure, image reduction, transfer, and cleaning, the photoreceptor without the usual protective f1 layer showed white streaks and no white streaks after 60,000 copies. Although black streaks were generated, the photoreceptor of the present invention was able to produce 120,000 copies with good image quality and no disturbances.

Example 2 2.4 parts by volume of γ-glycidoxyprobyltriethoxysilane, 6.6 parts by volume of methyltrimethoxysilane, 2.4 parts by volume of trimethylmethoxysilane, N-(β-aminoethyl)γ-amino Propyl trime 1-xysilane 1.2
Volume parts and 1.2 volume fi parts of γ, γ, T-trinololopropyltriethoxysilane were mixed, 1.2 volumes of water was added thereto, and immediately 50 volume parts of ethanol was added to form a coating solution for forming a protective layer. was prepared. The above-mentioned protective layer-forming coating solution was applied onto a known electrophotographic photoreceptor in which an organic compound was provided on an aluminum support, and this was heated at 80°C for 10 hours to form a transparent wear-resistant protective layer. Ta.

The thickness of this protective layer was 0.8 μm.

As a result of charging and removing static electricity and leaving it in an ozone atmosphere, the retention rate was 2! The photoreceptor without a layer had image disturbances after 8 hours of continuous use, but the photoreceptor of the present invention produced good quality copies without any image disturbances even after 48 hours.

In addition, the r & ] height of the protective layer was measured by the pencil hardness method.
There was 1C. Next, as in Example 1, the method was applied to electrophotography, and as a result, copies with good image quality were obtained without image disturbance even after 100,000 copies were made.

Comparative Example 1 β-(3,4-■Boxycyclohexyl)■Tiltrimethoxysilane 4.8 parts by volume, dimethyldimethoxysilane 2.4 parts by volume, γ, γ, γ, triflo [cobrovir trime 1 to xysilane 2. 4 parts by volume, 1.2 parts by volume of γ-7 minobrobyltriethoxysilane, 1.2 parts by volume of water, and then 50 parts by volume of ethanol to prepare a coating solution for forming a protective layer. did. Then fjfj! on an aluminum support. The above-mentioned coating solution for forming the third temple is applied onto a known electrophotographic photoreceptor provided with the compound, and
C. for 2 hours to form a transparent protective layer. The thickness of this protective layer was 1.0 μm.

As a result of a peel test of the adhesion of the cold insulating layer to the photoreceptor using cellophane tape, no peeled portion was observed. In addition, the hardness of the protective layer was examined using the pencil hardness method.
Met. Next, as a result of applying a known method to an electrophotographic method consisting of band'+b% exposure, image reduction, transfer, and cleaning, black streaks were generated on 80,000 copies of Photoreceptor 1 provided with the above protective layer. .

[Effect of the invention] 4
As mentioned above and as can be seen from the examples, the present invention includes J,
2 is formed! Depending on the layer, the obtained I'T R
The photoreceptor has the following effects and advantages.

(1) In the case of conventional A-type photoconductors, the surface deteriorates in an ozone atmosphere due to negative charging and image blurring occurs, but by providing the surface protective layer of the present invention, deterioration and blurring of the photoconductor surface can be prevented. , low resolution can be prevented.

(2) When polishing was performed by grade cleaning, etc., the marks conventionally appeared as streaks on the image, but by providing the surface protective layer of the present invention, local changes in the electrostatic voltage can be prevented and this cleaning can be performed. It is possible to obtain a photoreceptor that does not receive more than 1 laW.

Therefore, the present invention has the excellent effect of preventing surface deterioration due to ozone and the like, friction with paper, and abrasion caused by cleaning members, and maintaining high resolution.

The photoreceptor of the present invention has a high temperature and high temperature. It is extremely useful because it can withstand continuous copying in 111T-.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing one embodiment of the present invention. In the figure, 1 is an S conductive support, 2 and 3 are made of an organic compound, 2 is a charge generation layer, 3 is a charge transfer layer, and 4 is a protective layer.

Claims (2)

[Claims] (1) An organic photoconductive layer is provided on a conductive support, and on this organic photoconductive layer, (a) at least one epoxysilane compound selected from the following group A, (b) from the following group B. At least one selected alkyl alkoxysilane compound, (c) at least one perfluoroalkyl silane compound selected from the following group C, and (d) at least one aminosilane compound selected from the following group D, An electrophotographic photoreceptor provided with a protective layer formed from a composition containing as a main component Group A: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Group B: (R^4)_nSi (OR^4) ＿４＿－＿nC
Group; CF_3(CF_2)_n__2(CH_2)_2
(R^4)_n___1Si(OR^4)_3_-_n_
_1, Group D; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, in the above general formula, R^1 is a straight chain or branched alkyl having 6 or less carbon atoms, or -CH_2CH=CH-CH_2CH_2-, and R
^2 is a straight chain or branched alkyl group having 4 or less carbon atoms, R^3 is a straight chain or branched alkyl group having 4 or less carbon atoms, or is an OR^3^' group, and R^3^' is A straight chain or branched alkyl group having 4 or less carbon atoms, R^4 is a straight chain or branched alkyl group having 8 or less carbon atoms, and R^5 is a straight chain or branched alkyl group having 2 to 4 carbon atoms. can be,
n is an integer of 1 or less, n_1 is an integer of 2 or less, and n_2 is an integer of 9 or less. (2) The protective layer contains 2 to 10 parts by volume of an epoxysilane compound of group A and 2 to 10 parts of an alkyl alkoxysilane compound of group B.
Part by volume, perfluoroalkylsilane compound of group C 2 to 1
2. The electrophotographic photoreceptor according to claim 1, which is produced from a composition containing 0 parts by volume, 0.5 to 2 parts by volume of an aminosilane compound of group D, and 1 to 6 parts by volume of water.